Doped oxide for shallow trench isolation (STI)

ABSTRACT

The embodiments described provide methods and structures for doping oxide in the STIs with carbon to make etch rate in the narrow and wide structures equal and also to make corners of wide STIs strong. Such carbon doping can be performed by ion beam (ion implant) or by plasma doping. The hard mask layer can be used to protect the silicon underneath from doping. By using the doping mechanism, the even surface topography of silicon and STI enables patterning of gate structures and ILD 0  gapfill for advanced processing technology.

FIELD

This disclosure relates generally to semiconductor substrate processing and more particularly to processes of oxide in shallow trench isolation (STI).

BACKGROUND

Shallow trench isolations (STIs) are used to separate and isolate active areas on a semiconductor wafer from each other. STIs may be formed by etching trenches, overfilling the trenches with a dielectric such as an oxide, and then removing any excess dielectric with a process such as chemical mechanical polishing (CMP) or etching in order to remove the dielectric outside the trenches. This dielectric helps to electrically isolate the active areas from each other. As circuit densities continue to increase, the planarity of STI structures could impact patterning of polysilicon structures.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure will be readily understood by the following detailed description in conjunction with the accompanying drawings, and like reference numerals designate like structural elements.

FIGS. 1A-1D show cross-sectional views of STI structures in a process flow, in accordance with some embodiments.

FIGS. 2A and 2D-2F show cross-sectional views of STI structure in a process flow with carbon doping, in accordance with some embodiments.

FIG. 2B shows dopant profiles of doping by ion beams and by plasma doping, in accordance with some embodiments.

FIG. 2C shows RF power as a function of time for a pulsed plasma reactor, in accordance with some embodiments.

FIG. 3 shows a process flow of doping oxide surface of STI structures to improve uniformity of wet etch rate, in accordance with some embodiments.

DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

It is to be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of the disclosure. Specific examples of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. In addition, the present disclosure may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.

FIG. 1A shows a cross-sectional view of two shallow trench isolation (STI) structures, in accordance with some embodiments. The two STI structures include a narrow structure 110 and a wide structure 120. In some embodiments, the narrow structure 110 has a width in a range from about 30 nm to about 2000 nm. The STI structures are formed by using a hard mask layer 102 on a semiconductor substrate 100. The semiconductor substrate 100 includes silicon. Alternatively, the substrate 100 includes germanium or silicon germanium. In other embodiments, the substrate 100 may use another semiconductor material, such as diamond, silicon carbide, gallium arsenide, GaAsP, AlInAs, AlGaAs, GaInP, or other proper combination thereof. Furthermore, the semiconductor substrate may be a bulk semiconductor such as bulk silicon. The bulk silicon may further include an epitaxy silicon layer.

In one embodiment, a pad silicon oxide layer 101 is formed on the silicon substrate 100. The pad silicon oxide layer 101 is formed by a thermal oxidation process. In some embodiments, the pad silicon oxide 101 has a thickness ranging from about 50 angstroms to about 200 angstroms. In some embodiments, the hard mask layer 102 is made of silicon nitride and is formed on the pad silicon oxide layer 101. The hard mask layer 102 can be formed by a low pressure chemical vapor deposition (LPCVD) process. For example, the precursor including dichlorosilane (DCS or SiH₂Cl₂), bis(tertiarybutylamino)silane (BTBAS or C₈H₂₂N₂Si), and disilane (DS or Si₂H₆) is used in the CVD process to form the hard mask layer 102. In some embodiments, the hard mask layer 102 has a thickness ranging from about 400 angstroms to about 1500 angstroms. The hard mask layer 102 is then patterned to form a mask for shallow trench etching. Photoresist deposition, lithography and resist development, etching, and post-etch resist removal are involved in forming the hard mask. Alternatively, other dielectric material may be used as the hard mask. For example, silicon oxynitride may be formed as the hard mask.

In some embodiments, the shallow trenches have a depth in a range from about 0.20 microns to about 1 micron for isolation purposes. The shallow trenches are filled with one or more dielectric materials to form trench isolation features 110 and 120, referred to as shallow trench isolation (STI) as well. In some embodiments, a liner layer 103 is used to line the openings of the STIs. The liner layer 103 may be made of silicon dioxide with a thickness in a range from about 0 Å (no liner) to about 300 Å. The lining oxide may be formed by oxidation by using an oxygen gas, or oxygen containing gas mixture, to oxidized the silicon on the surface of the openings of the STIs. For example, the lining oxide layer 103 may be formed by oxidizing the exposed silicon in an oxygen environment at a temperature from about 900° C. to about 1100° C. An annealing process (or anneal) could be performed after the liner layer 103 is deposited to prevent crystalline defects due to the oxidation process.

The openings of the STIs are then filled with a dielectric gapfill layer 105. In some embodiments, the dielectric gapfill layer 105 is made of silicon oxide, which can be filled in the trenches by a CVD process. In various examples, the silicon oxide can be formed by a high density plasma chemical vapor deposition (HDPCVD). The silicon oxide may be alternatively formed by a high aspect ratio process (HARP). In another embodiment, the trench isolation features, 110 and 120, may include a multi-layer structure. In furtherance of the embodiment, the openings may also be filled with other suitable materials, such as silicon nitride, silicon oxynitride, low k materials, air gap, or combinations thereof, to form the trench isolation features.

After the dielectric gapfill layer 105 is deposited, the substrate may undergo an anneal to densify the gapfill layer 105 and to reduce its wet etch rate(s). The densification process can be performed in a furnace or a rapid thermal processing (RTP) chamber. In some embodiments, the post gapfill anneal is performed at a temperature ranging from about 900° C. to about 1100° C. in an RTP chamber for a duration from about 10 seconds to about 1 minute.

After the trench-filling is done, the substrate undergoes a planarization process to remove excess dielectric outside the STIs. In some embodiments, a chemical mechanical polishing (CMP) process is applied to the semiconductor substrate to remove excessive portions of the trench-filling dielectric material and to form a global planarized surface. As one example, the CMP process may use the hard mask layer 102 as a polishing stop layer so that the CMP process can properly stop at the hard mask layer 102. Other processes may be used to achieve the similar polishing effect. For example, an etch-back process may be used to remove the excessive trench-filling dielectric material and form a global planarized surface. FIG. 1B shows the structure of FIG. 1A after a CMP process using the hard mask layer 102 as a CMP stop layer, in accordance with some embodiments.

After the CMP is performed, a wet oxide etch may be performed to adjust the height of the dielectric material in the STIs in anticipation of the removal of the hard mask layer 102. The hard mask layer 102 and the pad silicon oxide layer 101 will be removed eventually, since they are sacrificial layers. In order for the surface of the substrate to be flat for easier and better photolithographical patterning, a portion of the oxide films in the trenches need to be removed. In some embodiments, the oxide removal is performed by a diluted HF dip. In some embodiments, the targeted amount of oxide removed is in a range from about 200 Å to about 1300 Å. FIG. 1C shows a schematic diagram of the structure of FIG. 1B after the dilute HF dip, in accordance with some embodiments. In some embodiment, the dilute HF is prepared by mixing HF with water at a ratio, such as 50:1 water to HF ratio. The dilute HF dip has a higher oxide removal rate of oxide in the narrow trench 110 than the wider trench 120. FIG. 1C shows that D1 (oxide etch depth in narrow shallow trench isolation 110) is larger than D2 (oxide etch depth in wider shallow trench isolation 120). In addition, at the corner(s) A of the wide STI 120, there is a V-shaped dip, which is also called an STI divot, which is a result of high local etch rate.

The higher etch rate could be a result of different degree of oxide density after the annealing (or densification process) described above. FIG. 1A shows a dotted line 108, which indicated a boundary of densification (by annealing) after gap fill of the STIs. The upper portion of the dielectric gapfill layer 105 is better densified than the lower portion of layer 105, which is separated from the upper portion by dotted line 108. A portion of the dotted line 108 remains after dielectric CMP, as shown in FIG. 1B. Both FIGS. 1A and 1B show that the dielectric gapfill layer inside the narrow STI 110 is not well densified. As a result, the etch depth D1 is larger than etch depth D1 due to higher etch rate of un-densified layer 105. FIG. 1B also show that a narrow portion near the corner(s) A of the wide STI 120 is not well densified, which results in the V-shape corner recess (or STI divot). The dilute HF dip creates a height difference between the wide and narrow STIs and also the STI corner recess (divot). After the dilute HF is performed to lower the surfaces of the STI structures, the hard mask layer 102 is removed by etching. Substrate 100 could undergo further processing until patterning of polysilicon to form gate structure. During these process operations, the there are wet processes used to remove dielectric layers, such as the removal pad oxide layer 101, and a sacrificial oxide layer (not shown) used in patterning and implanting the diffusion regions (also not shown). Such dielectric-removing wet processes further worsen the step height difference between the narrow STI and wide STI, and also the corner recess issue (STI divot). FIG. 1D shows the narrow STI 110 and wide STI 120 after the removal of the hard mask layer 102, the pad oxide layer 101, and also the deposition and removal of a sacrificial oxide layer (not shown), in accordance with some embodiments. FIG. 1D shows although the surface 131 of the wide STI 120 is at the same level as the surface 130 of silicon, the central surface of the narrow STI 110 is below the silicon surface 130 by a depth of D₃, which become quite significant after multiple wet etching operations. In addition, the divot at corner locations A is quite severe. The severe recess in the shallow STI 110 and the divot at corners “A” would severely impact the photolithography of the gate patterning and possibly inter-level dielectric (ILD) (or ILD0) gapfill between gate structures. Therefore, it's important to improve the wet etch uniformity between wide and narrow STI structures and also the corners of wide STI structures.

One way to reduce wet etch rate of oxide is by doping the oxide with carbon (C). FIG. 2A shows dopant being implanted into the surface of the substrate 100 after CMP, in accordance with some embodiments. The hard mask layer 102 may be used as a doping (or implant) mask to protect the silicon regions (active regions), B and C, underneath. The doping (or implant) of carbon may be performed by ion beams (ion implantation, or beam line) or by plasma implantation. FIG. 2A shows carbon ions 150, being directed toward substrate 100 and implanted into the surface of substrate 100, which include hard mask layer 102, liner oxide layer 103, and dielectric gapfill layer 105. If the hard mask layer 102 is made of silicon nitride, silicon nitride is harder to dope (or implant) than silicon oxide film(s). Only surface layer of the oxide film(s) needs to be doped. FIG. 2A shows the dopant has a thickness of T in the dielectric gapfill layer 105 and the liner layer 103, in accordance with some embodiments. The thickness T should be larger than the thickness T1 of the hard mask layer 102 after CMP and the thickness T2 of the pad oxide layer 101. Because the carbon dopants needs to be at the surface of the STIs 110 and 120 after the hard mask layer 102 and pad oxide layer 101 are removed to protect the STIs 110 and 120 from wet etch loss. In some embodiments, the thickness T is in a range from 200 Å to about 1300 Å.

If the doping is performed by ion beams, the dopants, which are ions, may be directed toward substrate 100 vertically (solid arrows), or tilted at an angle “α”. The angle may be about zero or greater than zero. In some embodiments, the angle is in a range from about 0° to about 60°. In other embodiments, the angle is in a range from about 0° to about 30°. Due to the relative shallowness of the doped layer 160, the doping energy is relatively low. In some embodiments, the doping energy is in a range from about 2 KeV to about 60 KeV. The dopant concentration is in a range from about 1E12 1/cm³ to about 1E17 1/cm³. In some embodiments, the temperature of the implant process is in a range from about −150° C. to about room temperature (about 25° C.).

As mentioned above, the doping may also be achieved by plasma doping (or PLAD). Since the plasma ions in the plasma sheath could move in different directions, not just directed towards the substrate as for the dopants from ion beams, the plasma ions 150 are illustrated by dotted arrows. Plasma doping (or PLAD) is ideal for shallow doping. The dopant plasma ions 150 arrive at the substrate surface in a range of angles, instead of being at a certain angle as in the case of ion implantation by ion beams. Plasma ions often have lower energy than the ions of ion beams. As a result, it's ideal for shallow doping. FIG. 2B shows dopant profiles as a function of depth for doping by ion beams and by PLAD, in accordance with some embodiments. Curve 210 shows a dopant profile by ion beams and curve 220 shows a dopant profile by PLAD. PLAD can have higher surface concentration with a more rapid decrease in dopant concentration with depth, which indicates better depth control for shallow doping. In contrast, ion beam doping is suitable for deeper implants. If the depth T of the doping is less than about 800 Å, PLAD is used, in accordance with some embodiments. For larger dopant depth, either doping method (ion beams or PLAD) is used. In some embodiments, a depth of the doped region is in a range from about 50 nm to about 800 nm.

Plasma doping is performed in a plasma doping system. An example of plasma doping systems is a PLAD system, made by Varian Semiconductor Equipment Associates Inc. of Gloucester, Mass. The doping gas is made by one or more carbon-containing gas, such as CH₄, C_(x)H_(y) (where x and y are integers), or a combination thereof. In some embodiments, x is in a range from 2 to 12 and y is in a range from 2 to 26. The doping gas may also include a carrier gas, such as H₂, He, Ar, Ne, Kr, Xe. The percentage of the carbon-containing gas may be in a range from about 1% to about 100%. In some embodiments, the process gas flow is in a range from about 50 sccm to about 500 sccm. In some embodiments, the pressure of the plasma process is in a range from about 5 mTorr, to about 50 mTorr. The RF (radio frequency) power is in a range from about 100 watts (W) to about 1000 W and at a radio frequency in a range from about 2 kilohertz (KHz) to about 13.6 megahertz (MHz), in accordance with some embodiments. The substrate may be or may not be biased. The dopant depth can be increased, if the substrate is biased. In some embodiments, the bias voltage is in a range from about 0 KV to about 10 KV. In some embodiments, the RF power supply can have dual frequencies. The doping plasma may be generated in the processing chamber or remotely (remote plasma). In some embodiments, the dosage of the dopant (carbon) is in a range from about 1E12 1/cm³ to about 1E17 1/cm³.

The radio frequency (RF) power for generating the plasma could be pulsed. FIG. 2C shows a diagram of power cycle of a pulsed plasma, in accordance with some embodiments. FIG. 2C shows that the RF power is turned on and off periodically. The duty ratio (power-on-time/total-time) of pulse could be in a range from about 5% to about 95% in accordance with some embodiments. In some embodiments, the plasma doping is performed for duration in a range from about 10 seconds to about 5 minutes.

After the doping is performed, the substrate is annealed to allow the carbon atoms to settle in the oxide layer, in accordance with some embodiments. In some other embodiments, the anneal operation can be skipped. The annealing temperature may be in a range from about 900° C. to about 1350° C. The annealing used may be performed by rapid thermal annealing (RTA) or by furnace anneal. Alternatively, the annealing process can be laser anneal or flash anneal. In some embodiments, the annealing time can be in a range from about 50 μs (micro seconds) to about 10 minutes. FIG. 2D shows that the substrate of FIG. 2A is annealed, in accordance with some embodiments. The heat can be provided to the front side of the substrate, backside of the substrate, or both front and back sides of the substrate. In some embodiments, this anneal operation can be skipped.

After the substrate is annealed, a dilute HF dip can be performed to reduce the height of oxide in the STIs. The oxide in the STIs is removed so that the substrate surface would be substantially flat after the hard mask layer 102 and pad oxide layer 101 are removed. FIG. 2E shows a cross-sectional view of substrate 100 after a dilute HF dip, in accordance with some embodiments. Due to the doping of carbon, the surface layer of the oxide film in both narrow and wide STIs has the same wet etch rate. As a result, the problems of higher etch rate in the narrow STIs and also at corners of wide STIs are resolved. The hard mask layer 102 protects the silicon underneath from being damaged by the doping process. FIG. 2E shows a cross sectional view of the substrate of FIG. 2D after a dilute HF dip, in accordance with some embodiments. The recess D11 in the narrow STI 110 and the recess D12 in the wide STI 120 are about the same. The reduced etch rate of carbon-doped oxide film makes controlling of the depths of the recess in narrow STI 110 and wide STI 120 easier and better. In addition, there is no STI divot in the corners of wide STI 120.

After the dilute HF dip, the hard mask layer 102 and the pad oxide layer 101 are removed. These two layers may be removed by dry etching and/or wet etching. FIG. 2F shows a cross sectional view of the substrate of FIG. 2E after the hard mask layer 102 and the pad oxide layer 101 are removed, in accordance with some embodiments. FIG. 2F shows that the surfaces 231, 232 of the STIs 110 and 120 are at about the same horizontal levels as the surface 233 of silicon. The surface layer(s) of the STIs 110 and 120 is doped by carbon, which protects the oxide in STIs 110, 120 from being excessively etched by subsequent wet etch processes.

FIG. 3 shows a process flow 300 of doping the surface of oxide in STIs with carbon to make the etch rate of surface oxide in narrow and wide STIs the same and without corner issues, in accordance with some embodiments. At operation 301, a substrate with STI structures are planarized with CMP to remove excess oxide outside the STI structures. At operation 302, the surface of the substrate is doped with carbon. The carbon doping can be performed by ion beams or by plasma doping (PLAD). After carbon doping, the substrate is annealed to allow carbon atoms to settle in the oxide film (or doped oxide layer) in the STIs at operation 303. In some embodiments, operation 303 is skipped and the substrate is not annealed after carbon doping. Afterwards, a dilute HF dip is performed to reduce the thickness of oxide in the STIs (to create recesses in the STIs) at operation 304. Since the removed oxide is carbon-doped, the removal rate is about the same in the narrow STIs and wider STIs. Further, the carbon doping resolves the issue or weak corners in wide STIs. After the HF dip, the hard mask layer is then removed at operation 305. The pad oxide layer may also be removed after the hard mask layer is removed.

The embodiments described above provide methods and structures for doping oxide in the STIs with carbon to make etch rate in the narrow and wide structures equal and also to make corners of wide STIs as strong as other surface portion of the wide STIs. Such carbon doping can be performed by ion beam (ion implant) or by plasma doping. The hard mask layer can be used to protect the silicon underneath from doping. By using the doping mechanism, the even surface topography of silicon and STI enables patterning of gate structures and ILD0 gapfill for advanced processing technology.

In one embodiment, a method of doping a surface oxide layer of shallow trench isolation (STI) structures on a substrate is provided. The method includes performing a chemical-mechanical polishing (CMP) on the substrate with STI structures, and the STI structures are filled with an oxide layer. The CMP is performed to remove the oxide layer outside the STI structures, and a hard mask layer used to as etching mask for forming the STI structures is used a CMP stop. The CMP forms flat surfaces on the STI structures with oxide on the flat surfaces. The method also includes doping the oxide on the flat surface on the STI structures with carbon atoms, and annealing the substrate after the doping is performed. The method further includes removing the hard mask layer.

In another embodiment, a method of doping a surface oxide layer of shallow trench isolation (STI) structures on a substrate is provided. The method includes performing a chemical-mechanical polishing (CMP) on the substrate with STI structures, and the STI structures are filled with an oxide layer. The CMP is performed to remove the oxide layer outside the STI structures, and a hard mask layer used to as etching mask for forming the STI structures is used a CMP stop. The CMP forms flat surfaces on the STI structures with oxide on the flat surfaces. The method also includes doping the oxide on the flat surface on the STI structures with carbon atoms, and removing the hard mask layer.

In yet another embodiment, shallow trench isolation (STI) structures on a silicon substrate are provided. The STI structures include a first STI structure, and the first STI is surrounded by silicon. The first STI structure is filled with silicon oxide; and a first surface of the first STI structure is at about the same level as a second surface of the silicon surrounding the first STI. The silicon oxide on the surface of the first STI is doped with carbon to reduce and control wet silicon oxide etch rate of the first STI structure. The STI structures also include a second STI structure, and the second STI is also surrounded by the silicon. The second STI structure is filled with the silicon oxide; and a third surface of the second STI structure is at about the same level as the second surface of the silicon surrounding the second STI. The silicon oxide on the surface of the second STI is also doped with carbon to reduce and control wet silicon oxide etch rate of the first STI structure.

Various modifications, changes, and variations apparent to those of skill in the art may be made in the arrangement, operation, and details of the methods and systems disclosed. Although the foregoing invention has been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein, but may be modified within the scope and equivalents of the appended claims. 

What is claimed is:
 1. Shallow trench isolation (STI) structures on a silicon substrate, comprising: a first STI structure, and wherein the first STI structure is surrounded by silicon, and wherein the first STI structure is filled with silicon oxide, and wherein a first surface of the first STI structure is at substantially the same level as a second surface of the silicon surrounding the first STI structure, and wherein the silicon oxide on the surface of the first STI structure is doped with carbon and a bottom portion of the first STI structure is free of carbon.
 2. The STI structures of claim 1, further comprising: a second STI structure, and wherein the second STI structure is also surrounded by the silicon, and wherein the second STI structure is filled with the silicon oxide; and wherein a third surface of the second STI structure is at substantially the same level as the fourth surface of the silicon surrounding the second STI structure; and wherein the silicon oxide on the surface of the second STI structure is also doped with carbon to reduce and control wet silicon oxide etch rate of the first STI structure, and wherein the second STI structure has width substantially larger than the first STI structure.
 3. The STI structures of claim 2, wherein the first surface of the first STI structure is at about the same level as the third surface of the second STI structure.
 4. The STI structures of claim 2, wherein the first STI structure has a width in a range from about 30 nm to about 2000 nm.
 5. The STI structures of claim 1, wherein a depth of the peak carbon dopant concentration in the first STI structure is in a range from about 50 nm to about 800 nm.
 6. The STI structures of claim 2, wherein the third surface of the second STI structure extends to the edge of the STI structure, and wherein the third surface is substantially planar without substantial dipping at the edges of the third surface.
 7. The STI structures of claim 1, wherein the second surface of the silicon surrounding the first STI structure is also doped with carbon.
 8. The STI structures of claim 1, wherein the first STI structure is lined with a liner layer with a thickness in a range from about 0 Å to about 300 Å.
 9. The STI structures of claim 8, wherein there is an interface between the liner layer and the silicon oxide used to fill the first STI structure.
 10. The STI structure of claim 8, wherein a surface region of the liner layer is doped with carbon.
 11. A semiconductor device area on a silicon substrate, comprising: a shallow trench isolation (STI) structure, wherein the STI structure is formed in the silicon substrate, and wherein the STI structure is filled with silicon oxide and a liner layer is located between the silicon oxide and the silicon substrate, and wherein a surface layer of the silicon oxide in the STI structure is doped with carbon, a surface layer of the liner layer is doped with carbon and a bottom portion of the liner layer is free of carbon.
 12. The semiconductor device area of claim 11, wherein a depth of the surface layer is in a range from about 50 nm to about 800 nm.
 13. The semiconductor area of claim 11, wherein a top surface of the STI structure extends to the edge of the STI structure, and wherein the top surface is substantially planar without substantial dipping at the edges of the top surface.
 14. The semiconductor device area of claim 11, wherein the top surface of the STI structure is at substantially the same level as a top surface of the silicon substrate surrounding the STI structure.
 15. The semiconductor device area of claim 14, wherein the top surface of the silicon substrate surrounding the STI structure is doped with carbon.
 16. The semiconductor device area of claim 11, wherein the liner layer has a thickness in a range from about 0 Å to about 300 Å.
 17. The semiconductor device area of claim 16, wherein there is an interface between the liner layer and the silicon oxide used to fill the first STI structure.
 18. The semiconductor device area of claim 11, wherein there is another STI structure in the semiconductor device area, wherein the other STI structure is also formed in the silicon substrate and filled with silicon oxide, and wherein a surface layer of the silicon oxide in the other STI structure is also doped with carbon, wherein the STI structure is substantially smaller than the other STI structure and a top surface of the STI structure is at substantially the same level as a top surface of the other STI structure. 